Thionitrosyl complexes reactions

A variety of routes is available for the preparation of metal-thionitrosyl complexes. The most common of these are (a) reaction of nitride complexes with a sulfur source, e.g., elemental sulfur, propylene sulfide or sulfur halides, (b) reaction of (NSC1)3 with transition-metal complexes, and (c) reaction of [SN]" salts with transition-metal complexes. An example of each of these approaches is given in Eq. 7.1,... 

Compared with the large number of nitrosyl complexes, only a few examples of thionitrosyl complexes have been studied. Although NS does not exist, a number of synthetic approaches to thionitrosyl complexes have been reported the reaction of nitrido complexes with S2CI2 or TMSNCS, treatment of chloro or 0x0 complexes with trithiazyl chloride or S(NTMS)2, or the use of heterocyclic nitrogen-sulfur rings. Pre-formed thionitrosyl cations in [NS][SbF6] or [NS)[AsFg] have been used to prepare the cationic complex [Re(NS)(CO)5] " in liquid S02. ... 

An Os phosphoraniminato complex has also been obtained via the reaction of an osmium(II) thionitrosyl complex with PPh3 (Equation (74)) " ... 

Thermolysis of (LH)2[RuCl5(NO)] (L = benzimidazole, imidazole, 5-nitrobenzimidazole, benzo-triazole, py) leads to the initial formation of [RuC NOJL]- with subsequent reaction to afford [RuCl3(NO)L2].M6 When solutions of RuCl with NaNCS in pyridine are refluxed for three days, a product formulated as [Ru(NCS)2py4] can be isolated.667 Nitrosyl and thionitrosyl complexes containing heterocycles with arsine or phosphine ligands have been reported.668... 

The photoinduced reaction of [CpCr(CO)a(NO)] with NO in hexane gives a mixture of [CpCr(NO)a]2 and [CpCr(N0)2(N02)]. The thionitrosyl complex [CpCr(CO)2(NS)l, having an essentially linear CrNS moiety, can be prepared from S3N3CIS and Na[CpCr(CO)3]. 4... 

Very recently, Seymore and Brown (873) reported that one of the products of the reaction of [TpOsNCy with [MoN(S2CNEt2)3] is the thionitrosyl complex [TpOs(NS)Cl2] (Eq. 188) presumably formed from dithiocarbamate cleavage. 

The related molybdenum thionitrosyl complex [Mo(NS)(S2CNEt2)3] has also been prepared in low yield as a result of a dithiocarbamate fragmentation process, after reaction of [Mo(N-p-tol)2Cl2(dme)] with 2 equiv of NH4S2CNEt2 (442). The precise nature of this process remains unknown, but the thionitrosyl ligand formally results from extrusion of the backbone carbon atom. 

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